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Dublin Institute of TechnologyMSc in Chemical and Pharmaceutical Process Technology
30-Apr-09
Preparation of Ultra Pure Water
A focus on Membrane Separations
by Pat Reynolds 30-Apr-09
Semiconductor
Power
Pharma
30-Apr-09 Dublin Institute of TechnologyMSc in Chemical and Pharmaceutical Process Technology2
Today’s Presentation
90%
• Introduction to pure water applications
• Pure water quality requirements– Semiconductor, Power, Pharmaceutical
• Water Contaminants
• Membrane Processes– MF, UF, RO
• Ion Exchange– EDI
• Semiconductor Industry Water– Water use Process Flow– UPW Process Flow
• High Efficiency RO (HERO)
• Q & A’s
30-Apr-09 Dublin Institute of TechnologyMSc in Chemical and Pharmaceutical Process Technology3
Introduction – Pure Water
• Semiconductor Industry– Ultra Pure Water (UPW) is used as an aggressive solvent to
wash a wafer many times during its fabrication.– Trace amounts of impurities in UPW can result in increased
defects and reduce yield
• Power Industry– Boiler feed water
• Pharmaceutical Industry– Purified Water – Wafer for Injection– GMP standards for production and quality
• A continuous supply of consistently pure water is critical to the profitability of a company.
30-Apr-09 Dublin Institute of TechnologyMSc in Chemical and Pharmaceutical Process Technology4
Semiconductor UPW quality requirements
• Table values ("targets") generally are typical levels, not best available technology
• Tables should be used as guidelines only, not as specifications. Every parameter for each application should be reviewed and justified.
International Technology Roadmap for Semiconductors (ITRS) 2006 www.public.itrs.net
30-Apr-09 Dublin Institute of TechnologyMSc in Chemical and Pharmaceutical Process Technology5
Reference only – refer to USP and Eur. Ph. For up-to-date figures
30-Apr-09 Dublin Institute of TechnologyMSc in Chemical and Pharmaceutical Process Technology6
Reference only – refer to USP and Eur. Ph. For up-to-date figures
30-Apr-09 Dublin Institute of TechnologyMSc in Chemical and Pharmaceutical Process Technology7
Reference only – refer to USP and Eur. Ph. For up-to-date figures
30-Apr-09 Dublin Institute of TechnologyMSc in Chemical and Pharmaceutical Process Technology8
Boiler Feed Water• Water contaminants must be limited to prevent scaling,
corrosion and foaming.– pH, Hardness, Oxygen, Carbon dioxide, Silicates, Dissolved
solids, Suspended solids, Organics
• Control limits– Conductivity is used as an indicator of total ion contaminants
with an upper limit of 1 mOhm-cm but plants usually operate at 5 to 10 mOhm-cm and 10 to 20 ppb silica.
– Other ionic contaminants listed above are usually < 2ppb
• Water Treatment includes– Reverse Osmosis– Ion Exchange– EDI
30-Apr-09 Dublin Institute of TechnologyMSc in Chemical and Pharmaceutical Process Technology9
Water Contaminants (1)-> S.E.M. -> OPTICAL MICROSCOPE -> VISIBLE TO NAKED EYE
MICRON
ANGSTROM
MOLECULARWEIGHT
->CLARIFIERS, MEDIA FILTERS
<---ULTRA---><---NANO---><---HYPER---> <---MICRO---> <------------------------------PARTICLE------------------------------>
-> RO'S
-> 0.1 PORES
-> 0.01 PORES -> BAG FILTERS, CARTRIDGE
<-POLLENS-><-BEACH SAND->
EXAMPLES
<-HUMAN HAIR->
->ENDOTOXIN, PYROGEN<-'
<-COAL DUST->
<-METAL IONS->
<-BACTERIA->
-> LOW PRESSFILTRATION
TECHNOLOGY
<-AQUEOUS SALTS-><-COLLOIDS-><-VIRUSES->
200 20,000 200,000 2,000,000
10,000 100,000 1,000,000 10,000,0001 10 100 1,000
1 10 100 10000.0001 0.001 0.01 0.1
SUSPENDEDDISSOLVED
30-Apr-09 Dublin Institute of TechnologyMSc in Chemical and Pharmaceutical Process Technology10
Water Contaminants (2)
Dissolved Suspended
Charged Uncharged
Ions
Organics Organics Organics
Silica Silica Silica
Gases
Living particles (Bacteria, Fungi, algae etc.)
Non living particles (Sand, silt, precipitates)
30-Apr-09 Dublin Institute of TechnologyMSc in Chemical and Pharmaceutical Process Technology11
Water Contaminants (3)
Natural Organic Matter (NOM)
Humic Acids
Fulvic Acids
Colloidal Organic Carbon
Dissolved Organic Carbon (DOC)
Total Organic Carbon (TOC)Total Organic Carbon (TOC)
Polysaccharides
30-Apr-09 Dublin Institute of TechnologyMSc in Chemical and Pharmaceutical Process Technology12
Water Contaminants (4)
• Gases– Dissolved Oxygen – contributes to unwanted native oxide growth on silicon
wafers and must be minimized in UPW.– Carbon Dioxide (Alkalinity)
• Acts as a contaminant • Changes with pH
30-Apr-09 Dublin Institute of TechnologyMSc in Chemical and Pharmaceutical Process Technology13
Membrane Processes
Used across industry in
water purification
30-Apr-09 Dublin Institute of TechnologyMSc in Chemical and Pharmaceutical Process Technology14
Microfiltration/Ultrafiltration
Water Quality Multimedia MF UF
Turbidity (NTU)
0.5 < 0.1 < 0.1
SDI15 3 - 5 < 3 < 2
Filtrate Water Quality of membrane versus conventional pre-treatment
• Membrane Material– polysulfones, polypropylene, and polyvinylidene fluoride (PVDF).
• Physical configurations – hollow fiber, spiral wound, cartridge, and tubular.
• Particle removal capability– MF down to 0.1- 0.2 microns.– UF down to 0.005-0.01 microns.
• Driving force– Pressure or vacuum.
Microfiltration Modules
Tubular
30-Apr-09 Dublin Institute of TechnologyMSc in Chemical and Pharmaceutical Process Technology15
Ultrafiltration modules
30-Apr-09 Dublin Institute of TechnologyMSc in Chemical and Pharmaceutical Process Technology16
Osmosis
• The tendency of water to pass through a semi-permeable membrane, into a solution of higher concentration.
Strong salt solution
Pure WaterWater
Semipermeable membrane
Time = 0 Time = Equilibrium
30-Apr-09 Dublin Institute of TechnologyMSc in Chemical and Pharmaceutical Process Technology17
What is Reverse Osmosis? • Reverse osmosis is the reversal of the standard flow of materials
in osmosis
• Pressure is applied to over come osmotic pressure, reversing osmosis
• Flow from higher salt concentration to lower salt concentration side.
Apply Pressure
Semi permeable
• Flow rate of water through the membrane is pressure dependent reducing the cconcentration of salts in the pure water side of the membrane will be lower
• RO membranes are effectively non-porous. The transport of a molecule across the membrane is diffusion controlled as described the solution-diffusion transport equation
• Salt passage through the membrane is not a function of pressure, is only a function of salt concentration
30-Apr-09 Dublin Institute of TechnologyMSc in Chemical and Pharmaceutical Process Technology18
FORCES ACTING ON THE MEMBRANE
• Osmotic Pressure: The pressure differential across a semi permeable membrane, due to the salt concentration gradient.
• Applied pressure: e.g. head pressure
1000mg/l salt solution
300mg/l salt soln
Water
10psi
3psi
7psi
100mg/l TDS = 1psi
Water
4.6ft
2.3ft
2.3 ft water column = 1psi
1psi
2psi
1psi
30-Apr-09 Dublin Institute of TechnologyMSc in Chemical and Pharmaceutical Process Technology19
Applying pressure to reverse the natural process osmosis
1000mg/l salt solution
300mg/l salt soln
10psi
3psi
Water
1psi
91psi
83psi
2.3ft
90psi Time = 0 Time = Equilibrium
Osmotic pressure
Applied pressure
Net driving pressure
30-Apr-09 Dublin Institute of TechnologyMSc in Chemical and Pharmaceutical Process Technology20
Exercise
3000 mg/l 20 mg/l
200 psi
Osmotic PressureApplied Pressure
50 psi
NDP
a) Osmosis
b) Reverse Osmosis
??
?
?
?
?
30-Apr-09 Dublin Institute of TechnologyMSc in Chemical and Pharmaceutical Process Technology21
RO transport Equations 1a
• RO membranes are effectively non-porous. The transport of a molecule across the membrane is diffusion controlled as described the solution-diffusion transport equation
)( pLN Aw
• where NAw is the water flux through the membrane, Δp is the trans membrane pressure difference, Δπ is the difference in osmotic pressure between the feed and the permeate, and L is a constant describing the physical characteristics of the membrane itself
• Flow rate of water through the membrane is pressure dependent • Concentration of salts in the pure water side of the membrane will be lower
30-Apr-09 Dublin Institute of TechnologyMSc in Chemical and Pharmaceutical Process Technology22
RO transport Equations 1b
• Within the context of the solution-diffusion model used to describe transport in nonporous films, L is given by
RTl
DSVL
• where D is the water diffusivity in the membrane, S is the water solubility in the membrane, V is the molar volume of water, R is the ideal gas constant, T is the ambient temperature, and l is the membrane thickness
• For an ideal solution, with complete dissociation of salt ions, osmotic pressure is defined as
CRT
• where π is the osmotic pressure, C is the salt ion concentration, R is the ideal gas constant, and T is the solution temperature.
30-Apr-09 Dublin Institute of TechnologyMSc in Chemical and Pharmaceutical Process Technology23
RO transport Equations 2
• Salt passage through the membrane is not a function of pressure
• The salt flux is only a function of salt concentration
)( permeatefeeds CCBN
• where Ns is the salt flux through the membrane, B is the salt permeability constant describing the physical characteristics of the membrane, Cfeed is the salt concentration in the feed solution, and Cpermeate is the salt concentration in the permeate solution.
30-Apr-09 Dublin Institute of TechnologyMSc in Chemical and Pharmaceutical Process Technology24
RO transport summary
• Thin Film Composite - give high flux, can operate at feed pressure up to 35 bar
• RO membranes are effectively non-porous. The transport of a molecule across the membrane is diffusion controlled
• Flow rate of water through the membrane is pressure dependent • The salt flux is only a function of salt concentration in feed
Handbook of Industrial Membrane Technology, M.C.Porter, 1990
SEM image of cross-section of a thin-film composite membrane
30-Apr-09 Dublin Institute of TechnologyMSc in Chemical and Pharmaceutical Process Technology25
RO Equipment (1)• Water Quality Impacts
– Removal of dissolved solids (TDS reduction)– Removal of organics– Removal of silica (total SiO2 reduction)– Removal of other trace contaminants (i.e., boron, metals)
• Application Limitations– Is not an “absolute” treatment technology such as ion-
exchange (>99% for most ions, ~ 70-80% TOC)– Requires downstream treatment for contaminants (TDS,
TOC, SiO2, etc.) to achieve “ultrapure” water– Polymer membranes cannot tolerate oxidizers such as
chlorine, biocides, ozone– Reject stream (~ 25% of the feed) is near-saturation and
non-reclaimable– Chemical injection required: antiscalant, biocide, oxidant
reduction (bisulfite)– Periodic on-site membrane cleaning using aqueous
chemicals
30-Apr-09 Dublin Institute of TechnologyMSc in Chemical and Pharmaceutical Process Technology26
RO Equipment (2)
Segmented Ring
Pressure Vessel
Pressure Vessel
Permeate
Concentrate
Permeate Plug
End Cap
End Cap/Membrane Element Adaptor
Brine Seals
Interconnector
O-Ring
Thrust Collar
End Cap/Membrane Element Adaptor
Feed
CONCENTRATE
( WASTE, BRINE, REJECT)
RO SYSTEM
FEEDWATER PERMEATE
PERMEATE PERMEATE
CONCENTRATE
TWO STAGE
30-Apr-09 Dublin Institute of TechnologyMSc in Chemical and Pharmaceutical Process Technology27
RO membrane manufacture
• Hydranautics video of spiral wound membrane manufacture– http://www.membranes.com/
• Downloads– Download RO animation
• Dow Filmtec video of iLEC Interlocking Endcaps– http://www.dow.com/liquidseps/service/lm_install.htm
• iLEC Interlocking Endcaps Video
30-Apr-09 Dublin Institute of TechnologyMSc in Chemical and Pharmaceutical Process Technology28
Ion Exchange (1)• Water Quality Impacts
– Removal of dissolved solids (TDS reduction) as ionic species
– Removal of ionized organics (TOC reduction)– Removal of silica (dissolved SiO2 reduction)– Removal of other trace contaminants (i.e.
boron/borate)
• Application Limitations– Is an “absolute” technology, completely removes
ionic species until resins “exhaust.” Requires frequent regenerations in high TDS applications (i.e. water softeners, primary beds)
– Because of leakage/exhaust issues, requires two IX mixed beds in series between the RO system and wafer Fab users for UPW, either one in primary and one in polish systems, or two in polish systems. Use of EDI can replace primary beds.
– Polymeric resins cannot tolerate oxidizers such as chlorine, biocides, ozone
30-Apr-09 Dublin Institute of TechnologyMSc in Chemical and Pharmaceutical Process Technology29
Ion Exchange Beds (2)
Ca2+
Mg2+
K+
Na+
H+
Cl-
SO42-
NO3-
HCO3-
HSiO3-
OH-
Less affinity for ion
exchange sites so more difficult to
remove
Cation Exchanger Anion Exchanger
Affinity of ions
• Higher valence
• Higher MW
• Resin beads are made of Styrene and Di-vinyl-benzene with functional groups attached.
• Upon exhaustion all exchange sites are occupied by ions from solution and the bead is unable to remove additional ions.
• Regenerate with HCl and NaOH
• Analyse for Sodium, Silica and Boron – signal ion breakthrough and resin exhaustion.
Product Water>18 mOhms
(CH3)3N + OH
FOr Other Anion
Exchange
_
_
Na+OH-
SO3– H+
Na+
Or Other Cation
Exchange
H+Cl-
HB4O7-
30-Apr-09 Dublin Institute of TechnologyMSc in Chemical and Pharmaceutical Process Technology30
Ion Exchange Beds (3)
• Mixed bed ion exchange resins i.e. they each bed has anion and cation resin (60:40 ratio – anion has less capacity).
• Separate resin based on different densities
Anion resin
Cation resin
Hydrochloric acid
Caustic
Regeneration chemicals to AW
30-Apr-09 Dublin Institute of TechnologyMSc in Chemical and Pharmaceutical Process Technology31
Electrodeionistation (EDI)
Cl-, HCO3-, SO4
2-, Other Anions
Ca2+, Na+, H+, Other Cations
Feed Water
– – – – – –
+ +++++
Product Water>15 mOhms
Cation Concentrate
Anion Concentrate
Cathode
Anion Exchange Membrane
Anode
SALTSH+
OH-
Cation Exchange Membrane
• Water flows through the IX resin in the dilute chamber.
• Normal IX occurs to produce high purity water in the dilute chamber.
• Positive ions are drawn to the cathode through the cation selective membrane
• Negative ions are drawn to the anode through the anion selective membrane.
• The large electric potential between the electrodes cause water in the dilute chamber to split into H+ and OH- ions which regenerate the resin.
30-Apr-09 Dublin Institute of TechnologyMSc in Chemical and Pharmaceutical Process Technology32
EDI (2)
Advantages
• Replaces regeneration chemicals
• Continuously regenerates resin system
• Robust mechanical systems.
• High performance and low maintenance
• Easily expandable.
Disadvantages
• Consumes high amount of power.
• Lots of piping involved in process, prone to leaks.
• Lots of parameters to monitor during operations.
• Difficult trouble shooting
EDI
Anion Mem.
OH-H+
CL-
H+OH-
Cathode Brine
Anode
Brine
Ion Exchanger ResinIon Exchanger Resin
Dilute
PDrainBrine Pump
DiluteCation Mem.
Anion Mem.
CL-
CL-
+
+ + ++
- - - - -Na+
Na+
Feed
EDI Chemical Free , Stand-by Bed Free
Regeneration
Waste Water
HCl
NaOH
Product
Feed
Ion Exchange Beds
Presented at UPW Expo, Philadelphia, PA Apr 2001
30-Apr-09 Dublin Institute of TechnologyMSc in Chemical and Pharmaceutical Process Technology33
Typical Semiconductor Plant water use
BlendWater
Ultra Pure Water FAB
Cooling Towers
Air Scrubbers
Internal WaterTreatment
Internal Water Recycling
Internal Reclaim
CityWater
Application Water UseUltra-pure water 50 - 60%
Cooling towers 20 - 30%
Scrubbers 5 - 8%
Domestic, others 5 - 10%
Reclaim 20 – 30%
WWT Plant
30-Apr-09 Dublin Institute of TechnologyMSc in Chemical and Pharmaceutical Process Technology34
Typical UPW system – block diagram
MAKE UP
1st Pass RO is main treatment step.
Pre-treatment steps required
PRIMARY LOOP
2nd Pass RO and IX are main
treatment steps.
POLISH LOOP
IX and UF are main treatment
steps
FAB
HUPW70 C
UPW PlantReclaim Drain
ULTRAPURE WATER November 2004
30-Apr-09 Dublin Institute of TechnologyMSc in Chemical and Pharmaceutical Process Technology35
Typical UPW Plant Process Flow
http://www.liqui-cel.com/
30-Apr-09 Dublin Institute of TechnologyMSc in Chemical and Pharmaceutical Process Technology36
Flow Diagram of Primary System
2B3T RO MB
Reclaim System
Pretreatment
Conventional System
EDI System
RO EDIReclaim System
PretreatmentMB
(Cation, Degas, Anion)
Presented at UPW Expo, Philadelphia, PA Apr 2001
30-Apr-09 Dublin Institute of TechnologyMSc in Chemical and Pharmaceutical Process Technology37
EDI System - pre-treatment
ProductConc.
HF Type UFPore Size -- 0.02um
Raw Water
Backwash
Filtration
Tank
ULP-RO(Operating Press. --100 psi)
EDI
Drain
Perfect Pretreatment Free RO CleaningUltra Low Pressure RO Low Power CostChemical Free No IX Regeneration
Perfect Pretreatment Free RO CleaningUltra Low Pressure RO Low Power CostChemical Free No IX Regeneration
Presented at UPW Expo, Philadelphia, PA Apr 2001
30-Apr-09 Dublin Institute of TechnologyMSc in Chemical and Pharmaceutical Process Technology38
UPW process efficiency improvement• High Efficiency RO (HEROTM)
FEED PERM.
REJECTMAXIMUM Reject pH is 11 for Membrane Warranty
HARDNESS AND ALKALINITY REMOVAL
(WAC and/or SAC)
DISSOLVED GAS REMOVAL
(FDG OR GTM)
TDS REDUCTION (HERO)
ALKALI
• Operating at high pH (~ 11) is the significant increase in rejecting weakly ionised anions such as organics, silica and boron.
• Strongly ionised species are also better rejected at high pH levels resulting in lower ionic loads on ion exchange beds.
• Pretreatment of the HEROTM feed water to remove hardness (Ca2+, Mg2+) and alkalinity (CO2) eliminates the potential for scale forming on the RO membrane allowing operation at high recoveries and flux.
Patent holder – Deb Mukhopadhyay
30-Apr-09 Dublin Institute of TechnologyMSc in Chemical and Pharmaceutical Process Technology39
List of References• High-Purity Water Preparation for the Semiconductor, Pharmaceutical and Power Industries, Theodore H. Meltzer, Tall Oaks Publishing Inc. 1993
• Reverse Osmosis, A Practical Guide for Industrial Users, Wes Byrne, Tall Oaks Publishing Inc. 1995
• http://www.dow.com/liquidseps/
• http://www.membranes.com/
• http://www.liqui-cel.com/